Capacitor



Feb 26, 1963 lcHxRO sATo ETAL 3,079,537

CAPACITOR Filed Deo. 4. 1959 A lllt 3,079,537 CAPACHOR Ichiro Sato, Eiichi Okamoto, and Yasuo Seki, all of Company This invention relates to capacitors of the rolled type in which very thin films of metal and dielectric are used.

A capacitor in which an anodic oxide film is formed as a dielectric on a metal surface of tantaium, aluminum, zirconium or titanium etc., and with a semiconductor layer like germanium, or an insulator layer like magnesium fluoride, or their conjugate layer, coated on the anodic oxide film by a method of evaporation or cathode sputtering, and further with a conductive layer like aluminum formed thereon by the saine method, whereby the abovementioned basic metal and coated conductive layer constitute the two electrodes of the said capacitor, has the advantages of being usable at specially high or low temperatures since it does not have an electrolyte as does the usual electrolytic capacitor, of also having good temperature characteristics of capacitance and power factor, and of being stable without deterioration. The principles involved are explained in U.S. Patent No. 2,836,776, granted May 27, 1958.

Formerly where the coated conductive layer of aluminum applied by evaporation is regarded as an electrode, a practical method of providing a lead-out terminal is to bring into contact with said layer an organic insulating film, for example, a polyethylene terephthalate resin film on which aluminum has been evaporated. The aluminum evaporated layer formed on the resin film is regarded as an outlet leading wire for the electrode. Further, a metal leaf, such as silver, is brought in contact with one end of the evaporated layer, and has a metal wire connected to it which acts as the electrode terminal.

However, the above type terminal is not completely effective since an unstable contact between the metal leaf and the aluminum evaporated layer is formed, i.e., with an applied voltage portions of the evaporated layer and edges of the metal leaf selectively short circuit, causing these portions to disappear, and insulating pockets to be formed.

An object of the present invention is to provide a dry type capacitor using very thin metal films and having favorable temperature characteristics in which the connections to the electrodes may be easily made,

Another object of the invention is to provide a capacitor of the dry type having electrodes of very thin metal films in which the danger of short circuits in use is reduced and the effects are less harmful.

Another object of the invention is to provide a capacitor of the dry type having at least one very thin metal lm electrode with means for materially decreasing the resistance of said electrode.

The invention is illustrated in the single figure which represents a greatly enlarged cross section of a capacitor embodying the invention. The capacitor shown in the ligure is constructed of two different parts. One of them is composed of five parts as follows: the base metal 1 of tantalurn (aluminum, zirconium, titanium, or the like), an anodic oxide iilm 2 as a dielectric formed on the base metal 1, a layer of insulating material 3, such as magnesium iluoride, on the anodic oxide film 2, a semiconductor layer 4, such as germanium, which is deposited on the layer 3 of insulating material by vacuum evaporation, cathode sputtering, or the like, and a layer of conductive material 5, such as aluminum, which is deposited on the Patented Fei). 26, 1953 layer 4 by the same method as the semi-conductor 4. The above-mentioned base metal 1 acts as one electrode of the capacitor.

This first part of the capacitor is actually the effective part, the base metal 1 and the conductive layer 5 forming the two electrodes. However, since the layer 5 is extremely thin, it is not only difficult to make connection to it, but it ha-s a considerable resistance so that other means must be provided to obtain -a uniform potential difference between corresponding points on the two electrodes. Moreover it is diiiicult to protect the film against damage in rolling the capacitor. These 'difficulties are solved by the addition of the second part of the capacitor.

This second part of the capacitor is composed of four parts, as follows: the base metal 9 which is different from the above-mentioned base metal 1, an anodic oxide layer 8, formed on the -base metal 9, a layer of an organic insu` lating material 7 on the anodic oxide layer 8, and a layer of conductive material 6 on the layer of an organic insulatin g material 7.

One end of the layer of the conductive material 6 is then brought into contact with the base metal 9. The capacitor is completed by bringing the layers of conductive :materials 5 and 6 of the two different parts into Contact with each other.

The layer of organic insulating material '7 is used to improve the mechanical properties of the oxide layer 8. If the anodic oxide layer S is not present or is imperfect for insulating purposes, instantaneous spark caused by a short circuit at the imperfect parts of the anodic oxide film 2 will be apt to make the base metal 9 irregularly deform by thermal and mechanical shocks and contact with the so deformed base metal 1, and so self-healing action, which is found in the case of metallized paper capacitors cannot be obtained.

But if the layer of organic insulating material 7 is applied on the anodic oxide layer 3, the layers 7 Iand 3 together will withstand the shock of the above-mentioned spark caused by a short circuit between the base metal 1 and the layer of conductive material 5, and only a limited `area of the thin layers of conductive materials 5 and 6 around the spark point is destroyed and so the short circuit is self-healed.

The layer of organic insulating material 7, by itself, has poor tensile strength and elasticity in a membranous state 'and is delicate in rolling operations. But when it is coated and combined on a metal surface having anodic oxide film, it can be satisfactorily used. Organic insulating material, such as silicon resin, that is too hard to make a thin and strong film by itself, but has superior thermostability, can also be used, and the deformation of the layer of organic insulating material by expansion and contraction due to heat is reduced, because it is coated and combined with the porous surface of the anodic oxide lilm according to the invention.

The metal layer 9' acts as the actual lead-in for the electrode 5, since the coating 6, is a very thin vacuum evaporated metal lm. Hence the coating 6 must be short circuited to the metal 9, and in such a construction, a good effect is obtained. The high electrical resistance between the ends of the layer of conductive material 5v can be remarkably lowered by the short circuit of the layer 6 to the metal 9 through the entire surface.

The anodic oxide film S is formed, for instance, of the so-called Alumite .'hich is in an extremely porous state. The layer 7 is produced thereon in a pinhole state according to a known method. Hence, when the conductive layer 6 is applied by a method, as, for instance, vacuum evaporation, evaporating metal grains get into the holes, and thus the conductive layer 6 and basic metal 9, not only come into contact electrically with each other at the one end, but also come into contact all over the surface through the holes, and the electrical resistance between the ends of the evaporating conductive layer 6 is remarkably decreased. For instance, the resistance yis decreased from 1/5 toi/10 of the resistance of one formed With'a'n aluminum evaponating conductive layer fon ethylene tetraiiuo-- tion, after which layers' of magnesiumuoridg germa? niuin, and aluminum are formedfonsthe 'surface by vacuum evaporation. The tantalum leaf isj regardedlas-an anode. Anodic oxidation of an aluminum llea-fof 0202 nim. thicknessr is produced by direct current in sulphuric acid, which forms a so-called Alumitey film, after which a layer of silicon` polymer of04 mm'. t`o'0.06'm`rn. thicknessis applied tothe surface. j It.is;then heated and dried andan aluminum layer is formed'on itbyI evaporation. Byforming an aluminum ylayer onto-the. endportionat which point the lsilicon .polymeris vnot applied, an electrical4 connection is lmade between `it andthe .aluminum leaf.l Therrietal leaves thu'sjnished lare rolled together, and an anode terminal is made by Welding 'Kovar' alloy wire to one end of the tantalum leaf .which Wire is ledout for the'anode terminal'. A 'cathode terminal is provided .by Welding' Kovar alloyywire to oneend ofthe valuminum leaf. The; capacitor is` tlijenjsealed in a lc'y'flindi'ical metalcase by'usi'ng'glass terminals.y l .v n..

, The capacitor formed above 'had capacity of"1.5/p. F., andwithstood 35 v..,at'normal temperature. Whileapplyinga .voltageof v2() v. about vlllhours. at 20.9? Q.,an'd fboutS hours at 250,"- C., no 'increa'sefof'.leakage'cu-rrent, short circuit, or other abnormal occurrences could be observed., Up to the present,V the highest temperature to vwhich a solid `electrolyti c capacitor havirigan anodic oxide lm asadielectric couldbe' raised vfvfa's 150.'C.l i I f l, vIn theabove-mentioned Yexample ananodic oxide Vfilm wasftirstjfomed on .thesurffacefofI the aluminum leaf. When, howeven'a thickenedv coating of`silicon polymer Was applied directly to the aluminum leaf Vapproximately the same'result" was achievedv butv lthe'.thermostability seemed to besomewhat inferior. y

Fluo'rine polymers, Yalkyds polymers, and fran polymers etc., are also usabley as 'an organic insulating materialliowever, it hasnbeen found thatsilicon polymers are thelniostsuitable in order to produce acapacitor.with the best thermostability and one which isI stable .at high tem pei'aturel,V f s f. i.

vAlthough manifold layers of an insulator anda semiconductor on an anodic oxide film for the dielectric are preferred, anfinsulator layer alone, like ymagnesium liucride 'ans calcium fluoride; or a 'semicnduetor' layer alone, like'germanium and lead sulphate, arelfsuicient. But capacitors so made have the disadvantages'of being-'Somevi/hat'A unstable, befin'g'easy toshort circuit, andinmass `productiontending tofproducewa large rfraotioii of defectiv'e"s. Y l5". l'

,l While'we have described aboveth'e principles of our invention'in connection with speoiiicapparatus, it is to be lclearly lunderstood that this descriptionl islmade. only by Way of 'example and. not as a'limitation'to thc- 'scope of our invention asset forth in the objects thereof and in the accompanying claims.

What We claim iS:

1. A capacitor of the dry type comprising first and second juxtaposed parts, said irst part comprising a metal base, an anodic layer on said base, an insulating layer on said anodic layer, a semi-conductor layer on said insulatinglayer, and a metal layer on said semi-conductorlayer, and said second part comprising a metal leaf, a porous anodic layer on said metal leaf, a layer of insulating material having a plurality of pinholes on said anodic layer, and a film of metal deposited on said insulating layer by evaporation, whereby grains of the metal will penetrate the. holes in saidA porous anodic layer and said layer of insulating` material having the pinholes,v saidparts being juxtaposed with said last jmentionedV metal ,filmy of said secondpart incontact'vvith'said m'etaljlayerv of said first v2. A capacitor comprising a pair of electrodes at least one of which is a thin lilmfof metal, insulating means separating said electrodes, a metal leaf spacedfrom said thin lilrn of' metal, and separating meansA maintaining said film and leaf in spaced relation and comprising. an organic `insulating layer having a pluralityr of pinholesthereth-rough and means for yelectrically connecting4 corresponding points on said `iilmand saidleaf through said pinholes.

3. A capacitor as deiinedjinclaim ZAinMWhich the otherv of the'pair of electrodesis'ametal' leaf. with an anodic oxidefilm formed thereon.I i, r

4.- A-,capacitor a-s'delinefd in claim`2 further comprising aporous anodic layer onthe` metal leaf, the lastmentioned means v comprising lgrains of*` metaly extending through the'pinhol'es and the pores Iof saidporous, anodic 5. A capacitor, as," defined inclaim 4, in which the grainsof metal-.arepartof and auxiliary metal iilm deposited on the organic insulating Vlayermby evaporation,

6; Adry, electrolyiscapacitor comprsinsrst and second coexte'ns'ive parts, said first part comprising. a ymetal basi@ Seleted from tlielsrrnin` consisting .ofgtantalum zirconium, aluminum ,and titanium, an anodiooxide film on said base, an insulatingl'ayeronqsaidulilm, a `semiconductor layerY `on saidA insulatingvlayer andan/,aluminum film deposited 'on 4 said I 'serniconductorA- layer, said second Vpart cpmpriisinsametalileafiselected'from aditerentmealf lthe above group, Va porous anodi-cfoxide rfilm, on said leaf, a'layer ofpinsulating material having a plurality` of pinholes 'fharthruehon .Saldi .arHQdCtlm and being .Selected from the group consisting of silicon polymers, iiuorine polymers, `alkydsV polymers and yfuran polymers, and a lilm of'alurminum deposited ,onsaid insulating layeryvhereby finpf theralumirlmm' penetrate the pinholes in the `insulating layer andftlie holes inthe porous .anodic lm, said Parts, ibansiuxtaaved with Said aluminum hu of. said second part inj contact with the aluminumtilm of said first Part- References Cited in the tile of this patent. UNITED STATES PATENTS 1,901659-1 Liiienfeld ten-M May 2, i933 2,836,776 Yoshioki -May. 27, 1958 FOREIGN PATENTS l 160,620 Australia v Feb. 4, 1954 701353 Great-.Britain ,.f- Mar. 1o, .1954 

1. A CAPACITOR OF THE DRY TYPE COMPRISING FIRST AND SECOND JUXTAPOSED PARTS, SAID FIRST PART COMPRISING A METAL BASE, AN ANODIC LAYER ON SAID BASE, AN INSULATING LAYER ON SAID ANODIC LAYER, A SEMI-CONDUCTOR LAYER ON SAID INSULATING LAYER, AND A METAL LAYER ON SAID SEMI-CONDUCTOR LAYER, AND SAID SECOND PART COMPRISING A METAL LEAF, A POROUS ANODIC LAYER ON SAID METAL LEAF, A LAYER OF INSULATING MATERIAL HAVING A PLURALITY OF PINHOLES ON SAID ANODIC LAYER, AND A FILM OF METAL DEPOSITED ON SAID INSULATING LAYER BY EVAPORATION, WHEREBY GRAMS OF THE METAL WILL PENETRATE THE HOLES IN SAID POROUS ANODIC LAYER AND SAID LAYER OF INSULATING MATERIAL HAVING THE PINHOLES, SAID PARTS BEING JUXTAPOSED WITH SAID LAST MENTIONED METAL FILM OF SAID SECOND PART IN CONTACT WITH SAID METAL LAYER OF SAID FIRST PART. 